Dehydrogenation catalyst



Patented Apr. 24, 1951 UNITED STATES PATENT OFFICE DEHYDROGENATION CATALYST Henry 0. Mottern, Bloomfield, N. J assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application August 23, 1948, Serial No. 45,797

'7 Claims. 1 This invention relates to an improved catalyst and, more particularly to an improved catalyst useful in the dehydrogenation of alcohols.

It is well known that the dehydrogenation of I zinc oxide, cerium oxide, magnesium oxide, etc.,

attained considerable prominence as dehydrogenation catalysts. Various combinations of catalytic metals and difiicultly reducible metallic oxides have also been employed from time to time. It was found that difficultly reducible metallic oxides have a dehydrating as well as a dehydrogenating effect and that due to the dehydrating effect, considerable olefin was regenerated from the alcohol which reduced the overall yield of ketone. actions, additives such as the alkali] or. alkaline earth metal carbonates or hydroxides have been employed in conjunction with the difiicultly reducible oxide catalysts. In instances where these additives have been used it has been noted that they make the catalyst thermally less stable, thus reducing its life and increase the susceptibility of the catalyst to catalyst poisons.

The object of the present invention is to increase the activity of difiicultly reducible metallic oxide catalysts such as magnesium oxide, zinc oxide, and beryllium oxide as dehydrogenation catalysts particularly for the dehydrogenation of compounds containing secondary alcohol groupings.

Another object is to improve the stability of diificultly reducible metallic oxide catalysts at high temperatures. Still another object is to make these catalysts more resistant'to poisons, thus lengthening their active life.

.Another object of this invention is to provide a process for the dehydrogenation of alcohols wherein the lay-products are relatively clean, that is, free of ethers, hydrocarbons, resins, etc. These and other objects will be apparent to those skilled in the art from the following description.

. .These objects are accomplished by the following which, in its general aspect, comprises the preparation of a catalyst consisting of a major portion of an oxide of magnesium, 'zinc, and beryllium, and a minor portion of an oxide of zirconium, cerium, and thorium. The latter oxides are present in amounts ranging from 1 to weight per cent, preferably 6 to 12 weight per In an attempt to minimize these recent, based on the total weight of the combined oxides. It has been found that from 1 to 15 per cent by weight of at least one of the oxides of zirconium, cerium and thorium, based upon the total weight of the catalyst composition, greatly improves the action of the magnesium oxide, zinc oxide, or beryllium oxide as a dehydrogenation catalyst. The catalyst is particularly effective in the dehydrogenation of compounds having the formula:

where R may be an alkyl, ary1,'alkaryl, aralkyl or cyclo alkyl radical and R1 can be H, or an alkyl, aryl, aralkyl, alkaryl or cycloalkyl radical such as 7 methyl, ethyl, propyl, etc.; phenyl; benzyl, etc.; methyl, phenyl or cyclohexyl.

The improvement obtained by using less than 1% of zirconium oxide, cerium oxide, or thorium oxide, or mixtures thereof, is perceptible but not sufficient to be of any consequence, while the improvement obtained by using more than 15% of these oxides is not sufilcient over that abtained when using about 6 tol2% to Warrant 'the additional expenditure.

It also has been found that'catalysts of the type described can be further stabilized by the addition thereto of approximately fi to 10% based on the Weight of the ziconium axide, cerium oxide, or thorium oxide, of a stabilizer selected from the group consisting of ferric oxide silica, and alumina.

The catalyst prepared from ZnO, MgO or'BeO and one of the three oxides of zirconium, cerium or thorium shows a high activity for dehydrogenation of pure secondary and low molecular weight primary alcohols. Pure feeds to a dehydrogenation process are not the general rule and in order to overcome the deleterious effect of impurities in the alcohols which resinify or carbonize under the conditions of dehydrogenation other metallic oxides have been added to the promoted zinc oxide catalyst. The catalyst prepared from the two oxides is inactivated by carbon or resin deposition unless small amounts of Si02, A1203 or FezOs is also included. Primary alcohols above Cs and polymeric olefins promote catalyst in activation when present as impurities in the alcohol to be dehydrogenated.

PREPARATION OF CATALYST The preparation of the catalyst of this invention may be exemplified by the preparation of a zinc oxideezirconium oxide catalyst.

There. are various types of zirconia which may be employed in the preparation of the zirconia containing catalyst of this invention. Typical U analyses of some of the grades of zirconia suitable are as follows:

1 A grade of zirconia manufactured by the Titanium Alloy Manufacturing Company, Niagara Falls, N. Y.

It has been established, however, that the catalytic effect of the zirconia added to the oxides of zinc, magnesium or beryllium, is due to the zirconium oxide itself, and not to the impurities contained therein. This was demonstrated by an experiment employing pure zirconium oxide as the additive to ZnO. In the preparation of the catalyst, it is preferred to mix the two oxides in the proper proportions in powdered form, then to work enough water into the mixture to make a heavy slurry of about the consistency of heavy cream. This will ordinarily require a volume of water approximately equal to the volume of powder employed. The catalyst slurry is then coated on a carrier. The coating may be accomplished by placing the catalyst support or carrier in a tumbling device, pouring the catalyst slurry over the carrier, and then tumbling until a uniform thick mix is secured. The mix is then placed in an oven at a temperature of about 80 C. and dried. The drying requires approximately 24 to 48 hours. Metal turnings may be employed as the catalyst carrier or support, although pumice in granular or pill form may be used as well as other types of carriers which are well known in the catalyst art. Pumice and metal turnings are preferred carriers, however, and of the metal turnings, steel or brass turnings are preferred.

CATALYTIC DEHYDROGENATION The catalyst of the present invention is particularly suitable in the dehydrogenation of secondary alcohols such as isopropyl alcohol, secondary butyl alcohol, secondary amyl alcohol, .etc., to the corresponding ketones. The conversion of secondary alcohols to ketones is accomlished by passing the alcohol in vapor form through. a catalyst packed tube heated to a temperature of about 400 to 1000 F., preferably 600 to 900 F., at a pressure of from 1 to 2 atmospheres, and a feed rate of from 0.5 to volumes, preferably 1.5 to 3 volumes, of liquid alcohol per volume of catalyst per hour. The pressure preferably employed during the reaction is held between atmospheric pressure and about 19 p. s. i. g.

Higher pressures are not desirable because decomposition seems to be more noticeable when the reaction occurs at the higher temperatures. The product vapors are passed to a condenser where the ketone and unreacted alcohol are condensed from the less readily condensible gas con sisting predominantly of hydrogen and a small amount of olefin hydrocarbon.

The alcohols employed in the dehydrogenation process may contain up to 10 to 12% of water without seriously affecting the dehydrogenation to the ketone'. The principal by-product resulting from the. dehydrogenation of secondary alcohols, according to this invention, has been found to be a high molecular Weight ketone of rather high purity. Thus, the by-product conglomerate usually recovered from the dehydrogenation of secondary alcohols is made well defined and easily recoverable by the use of the catalyst described. The formation of other by-products such as ethers, hydrocarbons, and hydrocarbon polymer resins, etc., is practically eliminated. The principal by-product resulting from the dehydrogenation of isopropanol to acetone has been identified as mesityl oxide, and that from the conversion of secondary butanol to methyl ethyl ketone as a C8 ketone in which 3-methyl heptene- 4 one-5 predominates. Small amounts of methyl heptanone-3 and ethyl hexanone-2 have been identified in the latter by-product.

The following examples which are included merely for purposes of illustration and not as a limitation, serve to demonstrate the effectiveness of the catalyst described for the dehydrogenation of secondary alcohols under the conditions indicated. The examples demonstrate the efiectiveness of the catalyst with respect to activity at high throughput, thermal stability, optimum temperature of reaction, long catalyst life, and resistance to poisons.

CATALYST ACTIVITY The following table summarizes experiments showing the efiectiveness of zinc oxide-zirconium oxide, zinc oxide-cerium oxide, and Zinc oxidethorium oxide catalysts in the dehydrogenation of alcohols:

.Table I Dehydrogenation of isopropanol (91-99%) over 94 weight per cent ZnOz6 weight per cent ZrOz (C. P. grade) P Per Cent Conversion to Conv. Acct n Mesityl o1 fin 0 i Oxide e Runs 31, 34 and 35 on 91% isopropanol; others on 99% isopropanol.

Dchydrogenation of 99% sec. BuOH over 94 Weight per cent ZnOzzG weight per cent ZlOz (C. P. grade) Dchydrog'cnation of 09% sec. BuOH over 94 weight per cent ZnOzfi weight per cent CeOz Per Cent Per Cent Yield Run No. v./v./hr. 2 5 5 M K EAK Olefin MEK 1. 5 750 94. 6 O. 24 U. 1 99. 6 6. 0 750 83. 7 98 4 98. 8 d. 0 900 90. .6 1. 3 6 98. 2 l. 5 750 60. 15 1. 61 1. 8 96. 7

5 '6 Table I-Continued THERMAL STABILITY AND CATALYST LIFE en ion f 99% s c. BuOH over 94 weight p In order to test'the thermal stability of the cent Z110 6 welght Per cent Thoz catalyst, tests were run for a period of five hours each at a temperature of 750 F., at a feed rate of 1.5, then at a temperature of 750 F., and a feed rate of 6.0, then at a temperature of 900 F., fi fi'k Ol fin MEX at a feed rate of 3.0, followed by a return to a temperature of 750 F., at a feed rate of 1.5. The

5 Per Cent} Per Cent Yield Ale 1.5 250 88.1 8.0 1.91 90.1 '10 runs in Table II demonstrate the thermal stag3 bility of the catalyst. It is estimated from the 1.5 750 62.2 1.7 life studies that the catalyst employed would last for three to six months without regenera- Dehydrogenation of 99% sec. BuOH over 94 weight per cent MgO 6 weight per cent Z102 (C..P. grade) Conversion M 1P '0 er Run N o. v./v./hr. Cent Mols to 8 83 3 Yield 1.5 MEK 6. 166 64. 2 96. G 114 9.49 111015 sec- 750 EAK 084 87 1. 3

BuOH fed. C4 Olefin.-. 144 1. 5 2. 25

Dehydrogenation of 99% isopropanol over 94 weight per cent MgO :6

weight per cent Z1'O (C. P. grade) tion. The runs also demonstrate the stability of the catalyst over a wide range of temperature.

Table II Rum. No. 79

Catalyst: 94 weight per cent ZnOzG weight per cent ZrO2 (Tamopax) Feed: 99% Isopropanol Catalyst on stream.

Feed Rate v./v./hr.

Temperature, F

"hours" M01 per cent Alcoho Acetone 87. 55. 8 82. 4 51. 7 IPOH 5. 43 40. 6 8. 18 41. 4 2. 15 67 7 56 5. 23 Mesltyl 5. 43 2. 91 1 81 1. 59 Per Cent Yleld Acet 0 94.0 89 8 88.2

Run No. 80

Catalyst: 94 weight per cent- ZnO:6 weight per cent ZrO2. (Zlrconla was a spectroscopic reference sample, more pure than C. P. grade) Feed: 99% sec-Butanol Catalyst on stream. hours 05 -10 l5 -20 Feed Rate, V./v. hr 1. 5 6.0 3. 0 1. 5 Temperature, 750 750 900 750 M01 Per-Cent Alcoh MEK 84. 5 62. 3 91.0 49. 2 2 33. 6 1. 48 46. 2 1. 52 68 5. 52 3. 8 13. 3. 4 1. 87 7 84.6 93. 8 92. 4 91. 5

Run N o. 83

Cata(l yst: 94 weight per cent 211026 weight per cent Zr 2 Feed: 91% Isopropanol Catalyst on stream .hours Feed Rate, v./v./hr Temperature, F. Mol Per Cent Alcohol Per Cent Convers on Table I I-Continued A B C D Run No. 70

Catalyst: 88 weight per cent ZnOz12 weight per cent Zr02 C. P. grade Feed: 91% Isopropanol Catalyst on stream hours. -5 -10 -15 -20 Feed Bate, v./v./hr 1. 5 6. 0 3.0 1. 5 Temperature, F 750 750 900 750 Mo] Per Cent Alcohol t0 4cetone 81.3 70.1 89. 8 86. 2 IPOH" 5.5 22.6 1.05 8.72 a= 1.4 .57 1.24 .97 Mesityl Oxide 11.75 6. 66 8. 42 4.04 Per Cent Acetone Yield 86.0 90. 6 90. 7 93. 4

Run N0. 71

Catalyst: 88 Weight per cent 2110:12 weight per cent ZrOz C. P. grade Feed: 99% sec-Butanol Catalyst on stream hours. 0-5 5-10 10-15 15-20 Feed rate, v./v./hr 1.5 6.0 3. 0 1. 5 Temperature, 750 750 900 750 M01 Per Cent Alcohol to:

MEK 90. 6 57. 2 95- 2 89. 0 sec-BUOH. 4. 68 41. 6 75 6. 5 Bu= 1.93 .64 2.0 2.1 EA: 1.9 .43 2.0 2.5 Per Cent MEK Yield 95. 1 97. 9 95. 9 95. 2

RZLIL N0. 74

Catalyst: 94 weight per cent ZnO:6 Z1'O2 (Tamopax) Feed: 99% sec-Butanol Catalyst on stream hours 0-5 5-10 10-15 15-20 Feed rate, v./v./hr 1. 5 6.0 3. 0 1.5 Temperature, F 750 750 900 750 M01 Per Cent Alcohol to:

MEK 86. 8 83. 5 85. 9 69. 6 sec-BuOH 1. 5 14. 0 9. 21. 2 u= 1.8 1.1 4.0 5.0 EA: 6. 9 1. 3 79 4. 1 Per Cent MEK Yield 88. 2 97. 1 94. 6 88. 4

For a given alcohol quantity the catalysts conmixture and 6 to 10% of silica based on the weight taining zirconium oxide, cerium oxide, and thorium oxide, exhibit marked resistance to poisons. For example, the secondary butyl alcohol employed in the runs described contained 91 to 99 weight per cent alcohol, 1 to 7.3 weight per cent impurities, and 0.3 to 1% water.

Having described the invention in a manner such that it may be understood by those skilled in the art, and having demonstrated the same by suitable examples, What is claimed is:

1. A dehydrogenation catalyst consisting essentially of a mixture of component A selected from the group consisting of zinc oxide, magnesium oxide and beryllium oxide, 1 to 15% of component B selected from the group consisting of zirconium oxide, cerium oxide, and thorium oxide based on the total Weight of the mixture, and 6 to 10% of at least one component C selected from the group consisting of silicon oxide, iron oxide and aluminum oxide based on the weight of component B.

2. A dehydrogenation catalyst of claim 1 deposited on a carrier.

3. A dehydrogenation catalyst of claim 1 deposited on steel turnings.

4. A dehydrogenation catalyst consisting essenconium oxide based on the total Weight of the of zirconium oxide.

5. The catalyst of claim 4 deposited on steel turnings.

6. A dehydrogenation catalyst consisting essentially of a mixture of zinc oxide, 6 to 12% of thorium oxide based on the total Weight of the mixture, and 6 to 10 of silica based on the weight of the thorium oxide.

'7. The catalyst of claim 6 deposited on steel turnings.

HENRY O. MO'I'TERN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,965,072 Dreyfus July 3, 1934 1,999,196 Lozier Apr. 30, 1935 2,039,543 Lorang May 5, 1936 2,217,009 Grosse et a1. Oct. 8, 1940 2,279,198 Huppke Apr. 7, 1942 2,395,876 Kearby Mar. 6, 1946 2,418,888 Kearby Apr. 15, 1947 2,436,733 Schneider et a1 Feb. 24, 1948 2,436,970 Mistretta Mar. 2, 1948 

1. A DEHYDROGENATION CATALYST CONISISTING ESSENTIALLY OF A MIXTURE OF COMPONENT A SELECTED FROM THE GROUP CONSISTING OF ZINC OXIDE, MAGNESIUM OXIDE AND BERYLLIUM OXIDE, 1 TO 15% OF COMPONENT B SELECTED FROM THE GROUP CONSISTING OF ZIRCONIUM OXIDE, CERIUM OXIDE, AND THORIUM OXIDE BASED ON THE TOTAL WEIGHT OF THE MIXTURE, AND 6 TO 10% OF AT LEAST ONE COMPONENT C SELECTED FROM THE GROUP CONSISTING OF SILICON OXIDE, IRON OXIDE AND ALUMINUM OXIDE BASED ON THE WEIGHT OF COMPONENT B. 